US2196580A - Production of useful chemicals from isomeric mono - nitro - ortho - dichlorobenzene mixtures - Google Patents

Production of useful chemicals from isomeric mono - nitro - ortho - dichlorobenzene mixtures Download PDF

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US2196580A
US2196580A US249542A US24954239A US2196580A US 2196580 A US2196580 A US 2196580A US 249542 A US249542 A US 249542A US 24954239 A US24954239 A US 24954239A US 2196580 A US2196580 A US 2196580A
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dichloro
nitrobenzene
mixture
chloro
nitrophenol
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US249542A
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Frank B Smith
John N Hansen
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Dow Chemical Co
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Dow Chemical Co
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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C201/00Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
    • C07C201/06Preparation of nitro compounds
    • C07C201/12Preparation of nitro compounds by reactions not involving the formation of nitro groups

Description

Patented Apr. 9, 1940 Tam oreica rnoono'rron or USEFUL CHEMICALS FROM ISOIWERIC MONO NITRO ORTHO DI CHLOROBENZENE MIXTURES Frank B. Smith'and John N. Hansen, Midland,
Mich assignors to The Dow Chemical Company, Midland, Mich.,'a corporation of Michig an No Drawing. Application'Jannary 5, 1939,
' Serial No. 249,542
6 Claims. (01. 260-422)" This invention concerns the conversion of a mixture of mono-nitro-ortho-dichlorobenzene isomers into valuable chemical agents which may readily be isolated as the pure compounds.
In the manufacture of 3,4-dichloro-nitrobenzene by nitration of ortho-dichlorobenzene, the
reaction product contains a major proportion of 3,4-dichloro-nitrobenzene and a minor propontion. of 2,3-dichloro-nitrobenzene. A part of the 3,4-dichloro-nitrobenzene in the mixture may 7 be separatedby fractional crystallization, leaving an eutectic mixture of 2,3-dichloroand 3,4- dichloro-nitrobenzenes. This eutectic mixture cannot readily be separated into its components by fractional distillation or crystallizationor by of 2,3-dichloro-nitrobenzene and 3,4-dichloro- 1 .nitrobenzene to hydrolysis the valuable products 2-chloro-4-nitrophenol and 2-chloro-6-nitrophenol may be formed in good yield, and that these products may be isolated without difliculty in pure form. The chloro-nitrophenol products are useful as chemical agents from which a wide variety of other products, e. g. resins, dyes, etc., may be prepared. The 2-chloro-4-nitro-phenol is particularly useful as a preservative against fungus attack on leather.
The mixture of isomeric dichloro-nitrobenzenes is hydrolyzed by heating the same with an aqueous alkali in the usual manner. The alkali employed may be sodium hydroxide, potassium hydroxide, calcium hydroxide, or other of the alkalies heretofore used for the hydrolysis of nuclear halogenated aromatic hydrocarbons. Usually between 1 and 2.5, preferably about 2, chemical equivalents of alkali are used per mole of dichloro-nitrobenzene, but the alkali may be employed in any other proportion desired. When used in a proportion less than that chemically equivalent to the-mixture of dichloro-nitrobenzenes, the 2,3-dichloro-nitrobenzene is hydrolyzed more rapidly than its isomer and partial separation of the 3,4-dichloro-nitrobenzene may be effected. Howeven'we prefer to employ sufficient alkalito hydrolyze both isomers and jected to hydrolysis.
subsequently to separate the phenolic products. The aqueous alkali is usuallyemployed in a concentration between 2 and 15 per cent byweight,
preferably between 5 and 10 per cent, but it may be used in lower or somewhat centrations, if desired.
The hydrolysis is accomplished by heating the reaction mixture under pressure in a closedre-v actor at temperatures of between and 200 0., preferably between and C. The reaction is usually complete. after from 5 to 10 hours of heating, although longer heating may in some instances be required.
."The reacted mixture contains the phenolic products in salt form, and the salt of Z-chlorol-nitrophenol usually crystallizes on cooling the mixture to room temperature or thereabout. In
. some instances, partial evaporation of the mixture'maybe desirable in order to obtain a good recovery of this crystalline salt. The crystalline salt is' separated from'the" liquor, washedwith water,acidified to liberate the 2-chloro-4-nitrophenol; and the latteris purified, when necessary,by crystallization, and dried. This Z-chloro--nitrophenol product is a white, crystalline ,material having a melting oint of 110.5 to
111C. The liquorjremaining after crystallizing the salt'of the 2-chloro-4-nitrophenol from the crude reacted mixture is extracted with a suitable solvent, such as benzene, chlorobenzene, ortho-dichlorobenzene, toluene,- xylene, etc., for
purpose of removing any unreacted dichloro-ni- An eutectic mixture containing about'60 per cent of 3,4edichloro-nitrobenzene and about 40 per cent of 2,3-dichloro-nitrobenzene was sub- 48 grams (0.25 mol) of this eutectic mixture, 21.3 grams (0.5 mol) of sodium hydroxide, and 245 cc. of water were heated together with stirring in an autoclave at a tem"- perature of 150 C, for 8 hours. The autoclave was then cooled and the charge removed. The reacted mixture was an aqueous slurry of orangecolored crystals of sodium.2-chloro-4-nitrophehigher conlization of the sodium 2-chloro-4-nitrophenolate was washed with chlorobenzene for purpose of extracting any unreacted dichloro-nitrobenzene therein. It was then rendered slightly acid by addition of a dilute aqueous nitric acid solution,v whereby 2-chloro-6-nitrophenol was liberated. from its sodium salt and precipitated in crude form as an orange-colored oil. The Z-chloro- G-nitrophenol was steam distilled from this oil and was subsequently purified by recrystallization from ethanol. It was obtained in the form of bright yellow crystals having a melting point of 70 to 70.4 C. The yield of 2-chloro-4-nitrophenol was approximately 50 per cent of theoretical, based on the proportion of 3,4-dichloronitrobenzene in the isomeric dichloro-nitrobenzene mixture initially employed, and the yield of 2-ch1oro-6-nitrophenol was. approximately 62 per cent of theoretical, based on the 2,3-dichloronitrobenzene in the same initial isomeric mixture. i
Although the method as hereinbefore described is usually applied in preparing ch1oro-nitrophenols from the eutectic mixture of dichloro-nitrobenzenes described in the above example, it is not restricted thereto. When desired, a mixture of 2,3-Zdichloronitrobenzene and 3,4-dihloro-nitrobenzene containing said compounds in any proportions may be subjected to the hydrolysis to produce the 2-chloro-4-nitrophenol and 2- chloro-G-nitrophenol products, and said products may be separated without difiiculty from one another by crystallization of their alkali metal or alkaline earth metal salts from aqueous solution. Also, the hydrolysis may, if desired, be carried out using an aqueous alcohol solution, e. g. a solution of methyl or ethyl alcohol, instead of water alone as the reaction medium,
Other modes of applying the principle of the invention may be employed instead of those exa mixture of 2,3-dichloro-nitrobenzene and 3,4-
dichloro-nitrobenzene to produce 2-chloro-6-nitrophenol.
2. The method which comprises hydrolyzing a mixture of 2,3-dichloro-nitrobenzene and 3,4- dichloro-nitrobenzene to produce 2-chloro-6-nitrophenol and 2-chloro-4-nitrophenol.
3. The method which comprises hydrolyzing a mixture of ,2,3-dichloro-nitrobenzene and 3,4-
dichloro-nitrobenzene and separating from the reacted mixture a product selected from the class consisting .of Z-chloro-i-nitrophenol and 2-chloro-6-nitrophenol. I
fl. The method which comprises hydrolyzing a mixture of 2,3-dichloro-nitrobenzene and 3,4- dichloro-nitrobenzene by heating said mixture of isomers with an aqueous base selected from the class consisting of alkali metal and alkaline earth metal bases at a temperature between 125 and 200 C.
5. The method which comprises hydrolyzing an isomeric mixture containing about 60 per cent by weight of 3,4-dichloro-nitrobenzene and about 40 per cent of 2,3-dichloro-nitrobenzene by heating the isomeric mixture with a dilute aqueous solution of an alkali metal hydroxide at a reaction temperature between about 125 and about 200 C. V
6. The method which comprises hydrolyzing an isomeric mixture containing about 60 per cent by weight of 3,4-dichloro-nitrobenzene and about 40per cent of 2,3-dichloro-nitrobenzene by heating said isomeric mixture at superatmospheric pressure to a reaction temperature between about 125 and about 175 C. with adilute aqueous solution of an1alkali metal hydroxide, and thereafter separating 2-chloro-4-nitrophenol and 2-chloro-6-nitrophenol from the reaction mixture. i
FRANK B. SMITH. JOHN N. HANSEN.
US249542A 1939-01-05 1939-01-05 Production of useful chemicals from isomeric mono - nitro - ortho - dichlorobenzene mixtures Expired - Lifetime US2196580A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3506724A (en) * 1966-09-23 1970-04-14 Fmc Corp Preparation of ortho- and para-nitrophenols
US3624164A (en) * 1966-08-04 1971-11-30 Du Pont Preparation of alkali metal salts of nitrophenols
US3928470A (en) * 1973-04-06 1975-12-23 Rhone Progil Preparation of 2-nitrohalophenols
US20050256343A1 (en) * 2002-07-10 2005-11-17 Eric Fache Process for preparation of a nitrophenol

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3624164A (en) * 1966-08-04 1971-11-30 Du Pont Preparation of alkali metal salts of nitrophenols
US3506724A (en) * 1966-09-23 1970-04-14 Fmc Corp Preparation of ortho- and para-nitrophenols
US3928470A (en) * 1973-04-06 1975-12-23 Rhone Progil Preparation of 2-nitrohalophenols
US20050256343A1 (en) * 2002-07-10 2005-11-17 Eric Fache Process for preparation of a nitrophenol
US20080045756A1 (en) * 2002-07-10 2008-02-21 Rhodia Chimie, Aubervilliers, France Process for preparation of a nitrophenol

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